CN1058032C - liquid stabilizer composition for halogenated polymers - Google Patents
liquid stabilizer composition for halogenated polymers Download PDFInfo
- Publication number
- CN1058032C CN1058032C CN93114480A CN93114480A CN1058032C CN 1058032 C CN1058032 C CN 1058032C CN 93114480 A CN93114480 A CN 93114480A CN 93114480 A CN93114480 A CN 93114480A CN 1058032 C CN1058032 C CN 1058032C
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- China
- Prior art keywords
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- composition
- chemical formula
- diketon
- grams
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 239000003381 stabilizer Substances 0.000 title claims description 27
- 239000007788 liquid Substances 0.000 title claims description 23
- 229920000642 polymer Polymers 0.000 title abstract description 6
- 239000000126 substance Substances 0.000 claims description 55
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- IFQULAPKPYIHBS-UHFFFAOYSA-N 1-phenyldecane-1,3-dione Chemical compound CCCCCCCC(=O)CC(=O)C1=CC=CC=C1 IFQULAPKPYIHBS-UHFFFAOYSA-N 0.000 claims description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 231100000252 nontoxic Toxicity 0.000 claims 1
- 230000003000 nontoxic effect Effects 0.000 claims 1
- 230000009967 tasteless effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 28
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 16
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000003512 Claisen condensation reaction Methods 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 71
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 150000002148 esters Chemical class 0.000 description 44
- 239000002904 solvent Substances 0.000 description 38
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 29
- 150000002576 ketones Chemical class 0.000 description 29
- 239000000463 material Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 22
- 239000011541 reaction mixture Substances 0.000 description 21
- -1 Zinic stearas Chemical compound 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 16
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 15
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 15
- 238000009835 boiling Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 13
- 239000008096 xylene Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 10
- 238000004313 potentiometry Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002075 main ingredient Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 125000005594 diketone group Chemical group 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- DBLXXVQTWJFJFI-UHFFFAOYSA-N 1-phenyloctadecan-1-one Chemical compound CCCCCCCCCCCCCCCCCC(=O)C1=CC=CC=C1 DBLXXVQTWJFJFI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000002085 enols Chemical group 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 2
- NCCNOQBFGNXMME-UHFFFAOYSA-N 1-phenylheptane-1,3-dione Chemical compound CCCCC(=O)CC(=O)C1=CC=CC=C1 NCCNOQBFGNXMME-UHFFFAOYSA-N 0.000 description 2
- KZMBNCLCSWGJDK-UHFFFAOYSA-N 1-phenyloctane-1,3-dione Chemical compound CCCCCC(=O)CC(=O)C1=CC=CC=C1 KZMBNCLCSWGJDK-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- HDNUKHUNPLPSQG-UHFFFAOYSA-N 1-phenylundecane-1,3-dione Chemical compound CCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 HDNUKHUNPLPSQG-UHFFFAOYSA-N 0.000 description 2
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XNCNNDVCAUWAIT-UHFFFAOYSA-N Methyl heptanoate Chemical class CCCCCCC(=O)OC XNCNNDVCAUWAIT-UHFFFAOYSA-N 0.000 description 2
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical class C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- UIXJZZFDIMBJTN-NTMALXAHSA-N (z)-2-(2-ethylhexyl)but-2-enedioic acid Chemical class CCCCC(CC)C\C(C(O)=O)=C\C(O)=O UIXJZZFDIMBJTN-NTMALXAHSA-N 0.000 description 1
- MNRBGFKCVTVNBA-UHFFFAOYSA-N 2-Hydroxyundecanoate Chemical compound CCCCCCCCCC(O)C(O)=O MNRBGFKCVTVNBA-UHFFFAOYSA-N 0.000 description 1
- ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 2-ethylhexanoic acid;zinc Chemical compound [Zn].CCCCC(CC)C(O)=O ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UXVMUIWCWJBWIY-UHFFFAOYSA-N 4-tert-butylbenzoic acid;zinc Chemical compound [Zn].CC(C)(C)C1=CC=C(C(O)=O)C=C1 UXVMUIWCWJBWIY-UHFFFAOYSA-N 0.000 description 1
- XVTWRQCEQFDSBK-UHFFFAOYSA-N 5-methyl-1-phenylhexane-1,3-dione Chemical compound CC(C)CC(=O)CC(=O)C1=CC=CC=C1 XVTWRQCEQFDSBK-UHFFFAOYSA-N 0.000 description 1
- IHLDEDLAZNFOJB-UHFFFAOYSA-N 6-octoxy-6-oxohexanoic acid Chemical compound CCCCCCCCOC(=O)CCCCC(O)=O IHLDEDLAZNFOJB-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- PIIOQYMDBKUPQJ-UHFFFAOYSA-N C(CCCCCCCC)C1=C(C=CC=C1)O.[Zn] Chemical compound C(CCCCCCCC)C1=C(C=CC=C1)O.[Zn] PIIOQYMDBKUPQJ-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003542 behavioural effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- DLAHAXOYRFRPFQ-UHFFFAOYSA-N dodecyl benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1 DLAHAXOYRFRPFQ-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- YBWHYYCPKWUPNW-UHFFFAOYSA-N formic acid;heptanoic acid Chemical compound OC=O.CCCCCCC(O)=O YBWHYYCPKWUPNW-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- VLHZUYUOEGBBJB-UHFFFAOYSA-N hydroxy stearic acid Natural products OCCCCCCCCCCCCCCCCCC(O)=O VLHZUYUOEGBBJB-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JZMYRQHKOYJYQO-UHFFFAOYSA-N methanol;1,2-xylene Chemical compound OC.CC1=CC=CC=C1C JZMYRQHKOYJYQO-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/12—Ketones containing more than one keto group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
- C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/07—Aldehydes; Ketones
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Abstract
The present invention relates to compositions comprising novel beta-diketones of formula or formula (II),
R1COCH2COR2(I)
R2COCH2COR2(II)
the composition can be used for stabilizing various polymers (such as polyvinyl chloride and PVC). The invention also relates to a process for the preparation of beta-diketones by the claisen condensation reaction, which can be represented as follows:
R4COCHR5H+R6C(O)OR7+RO-→[R4COCR5COR6]-+R7OH+ROH。
Description
The present invention relates to contain the composition of novel beta-diketon, described beta-diketon has following chemical formula (I) and chemical formula (II):
R
1COCH
2COR
2 (I)
R
2COCH
2COR
2(II) this based composition can be used for making various polymkeric substance to keep stable, for example polyvinyl chloride (PVC).The present invention also relates to by claisen (Claisen) condensation reaction to prepare the method for beta-diketon, this condensation reaction is shown below:
Beta-diketon is the compound that a class has extensive industrial use, for example is used for METAL EXTRACTION and polymer stabilising.Beta-diketon is the at present best organic stabilizer that is used for halopolymer (as PVC) that easily obtains.Therefore these compounds become more and more important industrial having become.
But the development of stabiliser composition does not produce the following composition that contains beta-diketon so far as yet, and this composition dissolves in the solvent of other additive in the stabiliser composition, and/or the beta-diketon composition is just as this solvent.The demand of the industrial liquid stabiliser composition of using for halogenated polymer increases, and this composition should be " single component " or " single component " prescription and do not produce undesirable smell.Up to the present be to come the obtaining liq stabiliser composition with the solvent that adds always, but the way that is to use this kind solvent has become inadvisable day by day, and this mainly is for to Occupational health and the concern that is stabilized the removal problem of contained volatile component in the polymkeric substance.
Thereby the beta-diketon composition had demand, this composition not only is liquid down in its use temperature (being generally room temperature), and even the single component liquid stabilising agent prescription that under bigger ratio, still can use with halopolymer in other batching miscible.
The advantage of low-viscosity (mobile) liquid product is very significant, below is a inventory of not enumerating fully:
-this product can measure and be injected in the polymer body with pump;
-this product can be immersed in the carrier, as neatly piece stone ore thing, CaCO
3, and calcium salt and zinc salt;
-can allow to adopt no dust operation, this has compared main advantages with diphenylpropane-1,3-dione(DPPO) (its limits of explosion is quite low) in non-food application.
But subject matter is manufacturing cost when the exploitation beta-diketon, because for example, this is very unpractiaca to use expensive stablizer in polymer industry.
At present the most frequently used method for preparing beta-diketon is the carbanion reaction of ester and a kind of ketone, and this is at European patent the 0th, 454, has disclosed in No. 623 (Ciba Geigy AG company) and the United States Patent (USP) the 5th, 015, No. 777 (Witco company).But the disadvantage of this method is to cause many side reactions, for example crotonization and generation 'beta '-ketoester.
For example at European patent the 0th, 454, in No. 623, once attempted to improve the productive rate of beta-diketon: promptly use dimethyl sulfoxide (DMSO) (DMSO, a kind of more expensive solvent), may also be added with ethanol with following way, at low temperatures, in the presence of sodium hydroxide or a kind of alcoholate, react.But the productive rate for ester then is a medium level.
Similarly at United States Patent (USP) the 5th, 015, in No. 777, solvent for use is not too expensive and more easily separate with unprocessed reaction mixture, but used ester is excessive greatly.The productive rate for ester is relatively poor by the time in being afterwards to remove alkyl benzoate.In addition, the resulting reaction mixture of low reaction productive rate just can not use without dynamical purification, and a large amount of excessive esters are wanted round-robin, and this is expensive often, undesirable in other words.
Therefore an object of the present invention is to propose a kind of stabiliser composition that contains beta-diketon, it is liquid under the composition use temperature.Another purpose of the present invention provides the stabiliser composition that contains beta-diketon, it with " single " component liquids stabilizer formula in other batching be partial miscibility at least.
A further object of the present invention provides the method that can obtain the beta-diketon high yield, and used reagent is relatively more cheap.Another object of the present invention provides the method that can obtain the high purity beta-diketon.
According to these and other purpose, first kind of embodiment of the present invention relates to the stabiliser composition that halopolymer is used, and it comprises at least a beta-diketone compound of effective quantity, and this compound is by chemical formula (I):
R
1COCH
2COR
2(I) or chemical formula (II):
R
2COCH
2COR
2(II) expression, R wherein
1By chemical formula
(Y)
n--expression, wherein are phenyl, and each Y (can be identical or different) is for hydrogen atom or be selected from group with next group: contain the hydrocarbon chain of 1 to 12 carbon atom, alkoxyl group, silyl and nonreactive activity halogen atom; Each R
2(can be identical or different) be represented hydrogen atom or is selected from group with next group: contain the hydrocarbon chain (can be one or more Sauerstoffatoms and be interrupted this chain) of 1 or 5 to 12 carbon atoms, aralkyl, alkoxyl group and silyl; An integer of n representative from 0 to 3; If its condition is the middle R of chemical formula (I)
2Carbonatoms less than 5, then contained the total number of carbon atoms is at least 3 among the Y, mostly is 12 most, and in chemical formula (II), two R
2The sum of middle carbon atom is at least 10.
Second kind of embodiment of the present invention relates to the method for the following beta-diketon of preparation chemical formula:
R
4COCHR
5COR
6This method is to be R by chemical formula
4COCHR
5The ketone of H and chemical formula are R
6C (O) OR
7Ester in the presence of alcoholate, react, the alcohol in the alcoholate is volatilizable under operational condition, R wherein
4And R
6(can be identical or different) respectively represents a hydro carbons group (can replace, the looping compound also can connect together), R
5Be hydrogen or alkyl; R
7Representation hydrocarbyl, and corresponding pure R
7OH is an evaporable under reaction conditions.
The third embodiment of the present invention relates to the beta-diketon that is generated by aforesaid method.
The 4th kind of embodiment of the present invention relates to the halopolymer that contains beta-diketon stabiliser composition of the present invention, especially polyvinyl chloride.
The present invention relates to the stabiliser composition of halopolymer (as PVC) usefulness.This stabiliser composition comprises at least a by chemical formula (I) of effective quantity:
R
1COCH
2COR
2(I) or chemical formula (II):
R
2COCH
2COR
2(II) Biao Shi beta-diketone compound, R in the formula
1Be expressed from the next:
(Y)
nThe of--wherein is a phenyl, and each Y (can be identical or different) is for hydrogen atom or be selected from group with next group:
-contain non-annularity hydrocarbon chain, alkoxyl group, the silyl of 1 to 12 carbon atom;
The halogen atom of-nonreactive activity; Each R
2(can be identical or different) be represented hydrogen atom or is selected from group with next group:
-acyclic contains hydrocarbon chain (also can be interrupted by at least one Sauerstoffatom), aralkyl, alkoxyl group or the silyl of 1 or 5 to 12 carbon atoms; N represents an integer of from 0 to 3, is preferably 0 or 1, and if its condition is the R of chemical formula (I)
2In carbonatoms less than 5, then contained the total number of carbon atoms is at least 3 in the Y group, mostly is 12 most, and in chemical formula (II), two R
2In the total number of carbon atoms then be at least 10.
Y is preferably the alkyl that contains 1 to 12 carbon atom.The total number of carbon atoms should be less than 6 in the Y group.This total number of carbon atoms is 3 better.Carbon atom among the group Y and R
2In the sum of carbon atom better less than 12, should be less than 10.
Wish that also one of Y group (or that unique Y) is in contraposition for the beta-diketon chain.
If hydrocarbon chain is linear, then R
2In carbonatoms should be between 5 to 9, with better between 5 to 7.If hydrocarbon chain branch, then R
2In carbonatoms should be between 5 to 12, with better between 5 to 9.If hydrocarbon chain is interrupted by an above Sauerstoffatom, then should have the interval of 2 carbon atoms between each Sauerstoffatom at least, just as in glyme.
To one skilled in the art, be easy to determine the consumption of beta-diketone compound in the stabiliser composition.Should comprise the beta-diketone compound of (calculating by mole) at least 2/3 in this stabiliser composition, 3/4 is better, and preferably 4/5.The main ingredient of this stabiliser composition is preferably the represented beta-diketon of chemical formula (I).
Except chemical formula (I) or (II) the main ingredient of beta-diketone compound as stabiliser composition of representative, said composition also should comprise at least a chemical formula (I), chemical formula (II) and/or other represented beta-diketone compound of chemical formula (III):
R
1COCH
2COR
1(III) each R wherein
1(can be identical or different) be identical with the above implication.
Special wish above-mentioned at least a chemical formula (I), (II), and/or (III) represented its total amount of other beta-diketone compound (joining in the polymkeric substance with main ingredient) is at least 5% of a main ingredient amount.The total amount of other beta-diketone compound is at least 10% better of main ingredient amount, preferably at least 15%.The consumption of each other beta-diketone compound can be determined by the skilled person.The total amount of the compound of chemical formula (III) expression should be no more than chemical formula (I) and the total amount of compound (II) represented 10%.
In general, toxicity linear increase and decrease with carbonatoms in the compound.Be that hanging down of the toxicity of beta-diketon composition of the present invention is wondrous, can hang down and can't measure unexpectedly.Some beta-diketon that does not belong to a part of the present invention has can not be ignored but lower toxicity.For example isovaleryl benzoyl methane is LD for the acute toxicity of mouse
50/ os=4885 mg/kg.What become sharp contrast therewith is that the toxicity of beta-diketone compound of the present invention then can be hanged down the degree of can not surveying.For R
1Be phenyl, R
2Be linear group (C particularly
7) compound, LD
50/ os generally surpasses 5000 mg/kg (mouse p.o.).
In addition, under the working conditions in PVC, beta-diketon composition of the present invention does not discharge smell basically, and this also becomes obviously contrast with close allied compound.In fact this point merits attention very much, because some lower homologue, for example R
1Be phenyl, R
2Be C
4(R
2=(CH
3)
2CHCH
2-) product, store or PVC takes place to decompose and emit and make us insupportable smell when transforming at composition.
In addition, with conventional wisdom among the one skilled in the art (be the diaryl beta-diketon, as diphenylpropane-1,3-dione(DPPO), when being arranged, iron produces very strong pigmentation as stablizer existence meeting, this may be because the strong absorption effects of chelate in 400 to 500 nanometer wavelength range) opposite, composition of the present invention can contain the diaryl diketone of higher proportion and not show hyperchromism.
The beta-diketon that is used for stabiliser composition should be liquid under 50 ℃ of temperature.This beta-diketon is that liquid is better under 30 ℃ of temperature, preferably is liquid down at 0 ℃.The beta-diketon of particularly suitable at room temperature is a liquid.
When being used as the homogeneous liquid additive of PVC, above-mentioned contain chemical formula (I) and/or (II) shown in the stabiliser composition of beta-diketone compound also should comprise at least a be selected from next group follow the use compound, wherein particularly be selected from zinc salt, alkaline earth salt and organic phosphite.What the one skilled in the art can select to suit at an easy rate follows compound to be included in the stabiliser composition of the present invention.The example of this compounds comprises zinc propionate, 2 ethyl hexanoic acid zinc, zinc laurate, Zinic stearas, zinc oleate, zinc ricinoleate, docosoic acid zinc, Zinc dibenzoate, p-tert-butyl benzoic acid zinc, zinc salicylate, single (2-ethylhexyl) MALEIC ACID, ZINC SALT, nonyl phenol zinc, and calcium, magnesium, barium and toxilic acid, acetate, oxalic acid, propionic acid, caproic acid, 2 ethyl hexanoic acid, capric acid, undecanoic acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, ricinoleic acid docosoic (docosoic acid), oxystearic acid, hydroxyl undecanoic acid, phenylformic acid, toluylic acid, the salt that generates between p-tert-butyl benzoic acid and the Whitfield's ointment also has the calcium that obtains from phenol and the phenols (as nonyl phenol) that replaced by one or more alkyl and the phenates of magnesium.
Beta-diketone compound total amount and above-mentionedly follow the ratio between the compound amount to be preferably at least 1: 100.This ratio be 1: 50 better, be preferably 1: 20.
The present invention also relates to the synthetic method of the following beta-diketon of chemical formula:
R
4COCHR
5COR
6This method is to be R by chemical formula
4COCHR
5The ketone of H and chemical formula are R
6C (O) OR
7Ester under alcoholate (alcohol wherein under the service temperature for volatile) effect, react.
R wherein
4And R
6(can be identical or different) respectively represents an alkyl, and the formation ring compound also can connect together;
R
5Be hydrogen atom or alkyl;
R
7Be alkyl, its corresponding pure R
7OH is volatile under reaction conditions.
R
4And R
6Be preferably the alkyl that contains 1 to 30 carbon atom, it is better to contain 1 to 18 carbon atom.R
4And R
6Preferably be selected from alkyl or alkenyl that linearity or ramose contain 1 to 24 carbon atom, contain the aralkyl of 7 to 10 carbon atoms, can contain one or more pairs key and respectively contain aryl or cycloaliphatic radical less than 14 carbon atoms.R
4And R
6Also can be the group that replaces, for example be replaced, can also in the fat carbochain, contain one or more-O-,-CO-O-,-CO-, and Si by halogen atom or alkyl (as methyl and ethyl).R in addition
4And R
6Also the divalent group that contains 2 to 5 carbon atoms can be formed together, a heteroatoms can also be contained, as oxygen or nitrogen.
R
5Being preferably hydrogen atom or containing the alkyl of 1 to 4 carbon atom, can be that replace or non-replacement, can contain one or more-O-,-CO-O-, and-CO-.R
5For hydrogen atom better.
R
7Be preferably the alkyl that contains 1 to 4 carbon atom.R
7For methyl better.
According to a kind of embodiment preferably of the present invention, the reaction mixture that is provided contains alcoholate, ester and solvent.In this mixture, add ketone, remove the alcohol that is generated simultaneously gradually.Ketone can add with pure state or with the solution form, can add separately or add with a part of ester in starting mixt not.
Ester can be used its simple shape, perhaps with its partially or completely from condensation product.According to a kind of embodiment of the present invention, if described ester is becoming with ester group at least one hydrogen atom is arranged on the alpha position, then this ester can partly use with the 'beta '-ketoester form of its generation at least, perhaps uses with the form of one of its esters.For example, if R
6Chemical formula can be write as
(R '
6) (R "
6) CH-then 'beta '-ketoester can be write as
R
6C (O) (R '
6) (R "
6) CC (O) OR
7R ' wherein
6And R "
6Can respectively do for oneself hydrogen or alkyl.This unexpected to result and the complete contradiction of the saying in the relevant technologies, so just may adopt the condition that helps generating 'beta '-ketoester can provide required beta-diketon because under suitable operational condition, add ketone.
Said alcoholate can be its corresponding alcohol volatilizable any alcoholate under reaction conditions, is preferably the alcoholate of basic metal or alkaline-earth metal.Described alcoholate with the alkoxide of basic metal or alkaline-earth metal for well.The alcoholate of particularly suitable is the alkali metal alcoholates that contains 1 to 4 carbon atom.The most suitable alcoholate is sodium methylate (sodium methoxide).
In the process of adding ketone, should under the solvent refluxing condition, remove the alcohol that is generated by distillation.Therefore temperature of reaction should be than at least 20 ℃ of this pure boiling point height.Temperature of reaction is at least 70 ℃ better, preferably is at least 100 ℃.In a kind of suitable especially embodiment of the present invention, range of reaction temperature is 100 ℃ to 200 ℃, with 110 ℃ to 150 ℃ better, pressure is normal pressure.
For present method pressure is not most important, but selects specified pressure can promote the quick removal of the alcohol that disengages in the reaction medium to a certain extent.If reaction is under reduced pressure carried out, then suitable range of reaction temperature is 80 ℃ to 150 ℃.
The mol ratio of ketone and ester should be less than 1, with between 2/3 to 1 for well.In general, used ester wants excessive 10% to 20% for ketone.
The stoichiometry mol ratio of ketone and alcoholate should be less than 1, with between 2/3 to 1 for well.In general, used alcoholate wants excessive 5% to 25% for ketone.
Selected solvent (can be pure substance or mixture) should have higher boiling point under normal pressure, so just can remove by various reactions disengage pure the time be unlikely solvent also taken out of.Thereby the boiling spread of wishing solvent under the normal pressure is 100 ℃ to 250 ℃, from 110 ℃ to 200 ℃ better.The boiling point of this solvent is preferably from 130 ℃ to 200 ℃.
Solvent and alcohol are fine to be separated in order to make, and the boiling point of solvent should be higher at least 20 ℃ than the boiling point of alcohol, with high at least 40 ℃ for well, preferably high at least 60 ℃.In addition, this solvent also can comprise and a kind ofly can form the material of minimum boiling point azcotrope as submember with alcohol; The boiling point of this azeotropic mixture should have enough big gap with the boiling point of reaction mixture so that its (this azeotropic mixture) can separate at an easy rate with the solvent in refluxing.
Be applicable to alcoholate the restricted condition of corresponding alcohol also be applicable to the corresponding alcohol of ester institute, just do necessary the correction in detail.Therefore for the alcohol in the ester, the boiling point of solvent also should be than pure R
7At least 20 ℃ of the boiling point height of OH to exceed at least 40 ℃ for well, preferably exceed 60 ℃ at least.
Wish to react the temperature of carrying out if the boiling temperature of solvent for use is higher than conventional personnel, any appropriate means of knowing in then available this area promotes the removal of alcohol, for example with rare gas element bubbling or operation under reduced pressure.
If solvent is made of single main ingredient, then should select not constitute the solvent of azeotropic mixture with the alcohol that is generated, can avoid a kind of situation like this, when promptly this azeotropic mixture refluxed, this alcohol entered in the reaction mixture again.Under another kind of mode, might when it disengages, just will contain pure azeotropic mixture gradually and remove.
The adding speed of ketone should be selected like this, promptly allows the pure content in the reaction medium keep low as far as possible, and hope can make in adition process that the ratio between the alcoholate and free alcohol is at least about 10 in the solution
3: 1, with 10
6: 1 is better, and preferably 10
9: 1.If temperature of reaction is lower than 70 ℃, then should reduce adding speed, for example be divided by as the factor with 2.
Its adding speed of the embodiment of the particularly suitable of present method is in the initial action mixture, every liter of alcoholate suspension, the per second bracelet is added 0.001 mole ketone most, and this speed can produce good result, if add speed for the highest 0.0002 mole/second/liter, then can obtain splendid result.
The third embodiment of the present invention relates to the beta-diketon that generates with above-mentioned the inventive method.
The 4th kind of embodiment of the present invention relates to the halopolymer that contains aforementioned stable agent composition.Know all for halopolymer (as PVC) and the method that adds stabiliser composition in the art.Can make halopolymer effectively stable stabiliser composition quantity all can adopt, determine that according to desired application the optimum consumption belongs in this area within the ken.
Following embodiment should not be counted as determinate just for the present invention is described.Without undue experimentation, the skilled person in this area can do various replacements and variation, and can implement substantially the same method and obtain the same basically result with the means of equivalence, and these all do not break away from notion of the present invention and purport.Embodiment 1: the physicochemical property of research beta-diketon
Table 1
By table 1 as seen, table two reference examples of below must discard.
| 180 ℃ of vapour pressure physical conditions of material smell (Pa) |
| Oenanthyl acetophenone 931 liquid; 11 ℃ of very weak decoyl acetophenone 745 solids of fusing point; " the strong dibenzoyl methanes of different valeryl acetophenone (contrast) 3724 liquid (contrast) 532 solids, 78 ℃ of fusing points are slightly for different 11 acyl acetophenones, 200 liquid of 33 ℃ of " different decoyl acetophenone 798 liquid " different nonanoyl acetophenone 532 liquid of fusing point " different caprinoyl acetophenone 266 liquid " |
Table 1 (continuing)
| Material | Solubleness in dioctyl phthalate (DOP) (DOP), gram/100 gram solvents | Solubleness in the single component additive, gram/100 gram solvents | ||||
| 23℃ | 3℃ | -15℃ | 23℃ | 3℃ | -15℃ | |
| The oenanthyl acetophenone decoyl acetophenone different decoyl acetophenone different nonanoyl acetophenone different different valeryl acetophenones of 11 acyl acetophenones of different caprinoyl acetophenone (contrast) dibenzoyl methanes (contrast) | ＞100 ＞100 | ＞100 50-100 | 50-100 12-25 | ＞18 ＞18 | ＞18 ＞18 | ＞18 9-18 |
| Dissolve each other under all proportions | Dissolve each other under all proportions | |||||
| 10-20 | " " " " about 10 | 5-10 | About 9 | ″ ″ ″ ″ 5-9 | ＜5 | |
Vapour pressure when table 1 has provided 180 ℃, this is the typical use temperature of PVC.
Branch's beta-diketon has solved the problem that is proposed well, though linear beta-diketon fusing point is near room temperature (9 ℃ to 33 ℃) but can be described as gratifying at least, because from the following stated visible they at dioctyl phthalate (DOP) (DOP, this is the softening agent of classics used among the PVC) and in " single component " or " single component " liquid stabilising agent prescription, have good solubleness.
Embodiment 2: the solubleness of The compounds of this invention
2.1. the solubleness in common solvent
Mixture of the present invention is at the following OBM that is called, and its diketone composition has following composition:
Capryloyl benzoyl methane 80%
Diphenylpropane-1,3-dione(DPPO) 6%
Two decoyl methane 4%
Caproyl benzoyl methane 6%
Two hexanoyl methane, 0.3% various inert impurities content account for 3.5%.
OBM and most of common solvent are dissolved each other fully in the time of more than 20 ℃.Its solubleness is more limited at low temperatures, and is as shown in the table:
Table 2
| Solvent | Solubleness under the differing temps (gram/100 gram solvents) | ||
| 22℃ | 5℃ | -10℃ | |
| Hexane toluene ethyl acetate acetone methylene dichloride ethanol | ＞100 ＞100 ＞100 ＞100 ＞100 ＞100 | ＞100 ＞100 ＞100 ＞100 ＞100 ＜20 | -15-15 50-100 25-50 50-100 are low |
These embodiment can be regarded as the test to the solubleness of composition of the present invention, but concrete data should be as being final conclusion property.In " single component " prescription, should avoid using solvent.
2.2. the solubleness in dioctyl phthalate (DOP) (DOP)
Directly the observation fusing point is subjected to the interference of supersaturation.For eliminating this influence, same mixture is adopted two kinds of methods:
Directly observe fusing point:
The various mixtures of OBM and DOP were deposited 4 days under to one of fixed temperature (22 ℃, 5 ℃ and-15 ℃), observed fusing point (seeing following table 3) subsequently, (S=is solvable in the table, and I=is insoluble).
Measure fusing point with differential thermal analysis (DTA):
Measure following 2 points:
-dissolving peak starting temperature (fusing starting point);
Temperature during-this peak maximum.
Suppose that actual solvent temperature is higher 4 ℃ than the starting temperature at peak, then can obtain the solubility curve of OBM in DOP.The mixture of representing with OBM of the present invention is with the preparation of the method among the embodiment 9, composed as follows by the diketone share:
Capryloyl benzoyl methane 80%
Diphenylpropane-1,3-dione(DPPO) 6%
Two decoyl methane 4%
Caproyl benzoyl methane 6%
Two hexanoyl methane, 0.3% various inert impurities content are 3.5%
Table 3
| Mixture | The solvability of observation | The fusing point that Differential scanning calorimetry is measured | Solvent temperature | ||||
| ％OBM | ％DOP | 22℃ | 5℃ | -15℃ | Initial | During peak value | |
| 100 95 90 85 80 70 60 50 40 30 20 10 | 0 5 10 15 20 30 40 50 60 70 80 90 | Limited S S S S S S S S S S S | I I I I I I I S S S S S | I I I I I I I I I I I S | 17.6℃ 14.2 13.9 12.3 10.3 9.6 4.4 0.2 -4.4 -7.7 - - | 28℃ 29.1 27.9 25.2 21.2 22.7 18.7 14.8 10.9 +5.7 - - | 22℃ 19 18 16 14 13 8 4 0 -3 ＜-15 |
Annotate: the solvable I=of S=is insoluble
Embodiment 3: the solubleness in the main ingredient of " single component " additive
Purpose be will be relatively based on the mixture of the present composition with based on the mixture of the diphenylpropane-1,3-dione(DPPO) behavioral trait when the preparation stabilizer blend.
Method:
-weighing mixture in the bottle of threaded block.
-bottle is placed on the shaking machine stirred several hours.
Table 4
Observed result
Annotate: Ba=p-tert-butyl benzoic acid barium.
| Prescription | The result | ||||
| Ba | Zn | Phosphorous acid ester | Beta-diketon | OBM | Diphenylpropane-1,3-dione(DPPO) |
| 0 0 0 0 0 1/4 1/8 1/10 1/10 1/10 | 2/3 0 0 1/2 0 1/4 1/8 3/10 2/10 3/10 | 0 1/3 2/3 0 1/2 1/4 3/8 3/10 5/10 0 | 1/3 2/3 1/3 1/2 1/2 1/4 3/8 3/10 2/10 6/10 | S S S S1 S S2 S S S S | I I I I I I I I I I |
The Zn=zinc octoate.
Phosphorous acid ester=phenylbenzene isodecyl phosphorous acid ester (alkylaryl phosphorous acid ester).
Beta-diketon=OBM or diphenylpropane-1,3-dione(DPPO).
The S=mixture is solvable.
The S1=mixture is solvable but be viscosity.
Solvable but the thickness very of S2=mixture.
The I=mixture is insoluble.Comparative examples 4: the solubleness of present used diketone (being diphenylpropane-1,3-dione(DPPO)) is being changed
In the formula (I), the R1=R2=phenyl.
Table 5
Table 5 footnote:
| Solvent | Solubleness (gram/100 gram solution) | ||
| In the time of 25 ℃ | In the time of 3 ℃ | In the time of-15 ℃ | |
| Epoxidized soybean oil, the ESO dioctyl phthalate (DOP), the DOP Octyl adipate, DOA trimellitic acid monooctyl ester, OTM trilauryl phosphite (2), " OS360 " tridecyl phosphite (2), " OS330 " phenyl didecyl phosphorous acid ester (2), " OS300 " phenylbenzene decyl phosphorous acid ester (2), the phosphorous acid ester of " OS150 " diethylene glycol monobutyl ether and dihydroxyphenyl propane (2) tetraline naphthane | 10-20 10-20 20-30 10-20 ＜10 ＜10 10-20 ＜10 10-20 20-30 5-10 | 10-20？(1) - 10-20 - - - 10-20 - 10-20 10-20 ＜5 | ＜1 5-10 5-10 5-10--＜10-Yue 10＜10 |
(1) this value possibility higher (crystallization is very slow, more than 1 month).
(2), only investigated concentration and be 10% and 20% solution for phosphorous acid ester.
These results can compare with result's (by of the present invention) of different capryloyl methyl phenyl ketone, under same temperature different capryloyl methyl phenyl ketone can any ratio and solvent above-mentioned mix.
Embodiment 5: oenanthyl benzoyl methane synthetic
Add following material in 2000 milliliters the Pyrex glass round-bottomed flask:
Freshly prepd sodium methylate 62.6 grams (1.16 moles)
715 milliliters of dimethylbenzene
Above mixture heating up to 100 ℃ added following material then in the clock time at about 10 minutes:
Pure enanthic acid formic acid 158.4 grams (1.10 moles)
The reacting by heating mixture is to refluxing (about 137 ℃), then under agitation, adds following material in 2 hours gradually:
Purified petroleum benzin ethyl ketone 120.0 grams (1.0 moles)
In all these steps, reaction mixture all remains under the inert atmosphere of nitrogen, and distill out dimethylbenzene-carbinol mixture so that the vapour temperature T that capital (pillar has a multi-layer braided fabric cover) distills (℃) in 108 ℃ to 115 ℃ scopes.The mixture that distills receives in the flask at a round bottom and reclaims.
Making the amount of solvent in the reaction medium keep constant by additional interpolation dimethylbenzene is about 715 milliliters.
Reaction medium keeps fluid and uniform state in whole process.
After adding the methyl phenyl ketone end, reflux and proceed 1 hour, distill out methyl alcohol in a small amount during this period again.The mixture that steams in entire operation comprises 140 gram dimethylbenzene and 62 gram methyl alcohol.Allow mixture cooling, under agitation change over to then and be placed with 800 gram ice and 38.6 milliliter of 95% sulfuric acid (contains 0.7 mole of H approximately
2SO
4) 2000 ml beakers in.Water is poured in the decant ampoule, respectively washs waters with 100 milliliters of dimethylbenzene twice then.The dimethylbenzene of washing usefulness merges with organic phase again, and uses 250 ml water washed twice respectively, dry and filtration on anhydrous sodium sulphate.
In this way obtain 1014 gram xylene solutions, measure with potentiometry and wherein contain 0.870 mole beta-diketon; The chemical yield of this expression beta-diketon is 87% (ketone with adding is benchmark).Potentiometry is also measured 0.170 mole carboxylic acid.
With stoichiometric sodium hydroxide (or yellow soda ash) extraction with aqueous solution carboxylic acid, and under reduced pressure remove after the dimethylbenzene, obtain thick product 217 grams of homogeneous phase oil form.
The gas chromatographic analysis (GC) of this product shown wherein contains following three kinds of beta-diketons (stabilization that can form of mixtures be used for halopolymer):
-oenanthyl benzoyl methane 182 grams (83.9%)
-diphenylpropane-1,3-dione(DPPO) 11.2 grams (5.1%)
-two oenanthyl methane 8.6 grams (4.0%)
This analysis confirmation total chemical yield be 87% (is benchmark with the ketone that adds).
The distillation of this reaction mixture is easy to realize, and obtains the mixture (productive rate is about 96%) that purity is about three kinds of beta-diketons of 99%.
Distillation also is used for separating pure oenanthyl benzoyl methane with higher yields (about 90%).This product is the water white oil form existence of 112 ℃ to 115 ℃ (under the 133Pa pressure) with boiling point.Its fusing point is 14 ℃, and its refractive index is 1.5558 in the time of 30 ℃, and its density is 1.004 in the time of 30 ℃.Nuclear magnetic resonance spectroscopy shows and wherein comprises 90% enol form and 10% diketone form.
Embodiment 6: oenanthyl benzoyl methane
Operation steps is with embodiment 5, and unique difference is only to add 144 gram (1 mole) Methylheptanoates.
Final xylene solution is shown that through potentiometric analysis and gas chromatographic analysis the beta-diketon productive rate is 81.1% (is benchmark with added ketone).
Embodiment 7: oenanthyl benzoyl methane (comparative example)
Operation steps is with embodiment 5, and unique difference is that what to be added is 316.8 gram (2.2 moles) Methylheptanoates.
Final xylene solution is carried out potentiometric analysis and gas chromatographic analysis shows that the beta-diketon productive rate is 94.8% (is benchmark with added ketone).
Also show with a collection of analytical results and only to stay 0.9 mole the ester that does not consume; Therefore be that the benchmark beta-diketon productive rate of calculating (promptly 72.9%) is starkly lower than the productive rate that obtains among the embodiment 5, i.e. 79.1% (supposing that all esters all consume among the embodiment 5) with the ester that is consumed.
So use excessive greatly ester can be attended by two great disadvantages:
-ester is wanted round-robin;
-beta-diketon productive rate (the ester amount with consumption is a benchmark) (this point can be explained with the generation by product) obviously on the low side.
Embodiment 8: capryloyl benzoyl methane
Add following material in the reactor of being introduced toward embodiment 5:
Freshly prepd sodium methylate 62.6 grams (1.16 moles)
715 milliliters of dimethylbenzene
Under dried nitrogen atmosphere with mixture heating up to 100 ℃, then in about 10 minutes clock times and go into following material:
Pure methyl caprylate 173.8 grams (1.10 moles)
The reacting by heating mixture is to refluxing (about 137 ℃), then under agitation, adds following material in 2 hours gradually:
Purified petroleum benzin ethyl ketone 120.0 grams (1.0 moles)
Following steps are identical with described in the embodiment 5 all.
The dimethylbenzene that distills and the weight of carbinol mixture are 203 grams (comprising about 140 gram dimethylbenzene and about 63 gram methyl alcohol).
Be recovered to 1033.3 gram xylene solutions, measuring with potentiometry wherein has 0.871 mole beta-diketon (expression is for the ketone that adds, and the chemical yield of beta-diketon is 87.1%).Also measure 0.170 mole carboxylic acid with potentiometry.
With stoichiometric sodium hydroxide (or yellow soda ash) extraction with aqueous solution carboxylic acid, and under reduced pressure remove after the removal xylene, obtain uniformly yellow liquid oily crude product 228 grams.
The gas chromatographic analysis of this product shows and wherein contains following three kinds of beta-diketons:
-capryloyl benzoyl methane 190.9 grams (83.7%)
-diphenylpropane-1,3-dione(DPPO) 12.4 grams (5.4%)
-two decoyl methane 10.8 grams (4.7%)
This analysis has affirmed that total chemical yield is 87% (is benchmark with added ketone)).
The distillation of this reaction mixture is easy to realize, and beta-diketon (about 94%) is separated with tar (about 6%).Distillation yield is about 97%, and products therefrom is analyzed its beta-diketon content greater than 99%.
Obtain pure capryloyl benzoyl methane by careful distillation yield (about 85%) separation preferably.Products obtained therefrom is the white solid form, fusing point lower (about 34 ℃), and boiling point is 121 ℃ to 122 ℃ (under 13.3Pa).Its refractive index (30 ℃) is 1.5445, and its density is 0.982 in the time of 30 ℃.Nuclear magnetic resonance spectroscopy shows and comprises 91% enol form and 9% diketone form in the product.
Embodiment 9: capryloyl benzoyl methane
Add following material in the embodiment 5 described reactors:
Freshly prepd sodium methylate 62.6 grams (1.16 moles)
150 milliliters of anhydrous dimethyl benzene
Mixture was heated to 100 ℃ under dried nitrogen atmosphere, added following material then in the clock time at about 10 minutes:
Methyl caprylate 189.9 grams (1.20 moles) that contain 6.8% methyl caproate
Reaction mixture is heated to backflow (about 137 ℃), then under agitation, adds following material in 2 hours gradually:
Purified petroleum benzin ethyl ketone 120.0 grams (1.0 moles)
Later step identical with described in the embodiment 5, just reaction mixture restrains H with 69
2SO
4(0.67 mole) acidifying, and with the washing of 100 milliliters of dimethylbenzene.
The gas chromatographic analysis of this product (in the time of about 24 ℃ fusing) shows and wherein contains following five kinds of beta-diketons:
-capryloyl benzoyl methane 80%
-diphenylpropane-1,3-dione(DPPO) 6%
-two decoyl methane 4%
-caproyl benzoyl methane 6%
Also comprise about 3.7% impurity in-two hexanoyl methane 0.3% this composition.
Embodiment 10 to 16:
Identical among operation steps and the embodiment 8, but some reaction parameter changes to some extent, that is:
The ratio of-reactant (excessive ester, excessive MeONa);
The time span of-adding methyl phenyl ketone.
Gained result (total chemical yield of beta-diketon) lists in the table 6 and (compares with embodiment 8).
Table 6
| Embodiment number | The parameter of revising: | |||
| Add Φ COCH 3Time | Add the ester amount | Add the MeONa amount | The beta-diketon productive rate is (with Φ COCH 3Be benchmark) | |
| 8 10 11 12 13 14 15 16 | 2 hours 2271222 | 1.1 mole 1.0 1.175 1.175 1.175 1.175 1.175 1.22 | 1.16 mole 1.16 1.16 1.16 1.16 1.025 1.075 1.16 | 87.1％ 80.0％ 88.7％ 88.4％ 82.7％ 88.5％ 89.5％ 88.9％ |
These results have confirmed following all points:
-when excess quantity when 0% is increased to 10%, the influence of excessive ester is very remarkable.
The influence of-excessive methanol salt is very little.
The influence of-joining day: 2 hours and 7 hour joining day provide substantially the same result.But add too fast (continuing 1 hour) result is had tangible disadvantageous effect; This is because for the methyl alcohol generating rate, the removal of methyl alcohol is fast inadequately.(ratio of MeOH and MeO＞1,000 this point is very important).
Embodiment 17: capryloyl methyl caprylate synthetic
Add following material in the embodiment 5 described reactors:
Freshly prepd sodium methylate 54.0 grams (1.0 moles)
715 milliliters of dimethylbenzene
Mixture heating up to 100 ℃ added following material then in the clock time at about 10 minutes:
Pure methyl caprylate 316.0 grams (2.0 moles)
Reaction mixture is heated to backflow (about 140 ℃), and the methyl alcohol that generated this moment is distilled out gradually.
The generation of finding formic acid is very slow.
Through 7.5 hours backflows with after removing methyl alcohol continuously, the quantity of methyl alcohol that steams is about 46 grams, the 10 gram dimethylbenzene of also having an appointment in its mixture.So far EO.
As reaction mixture being carried out obtaining the clarifying xanchromatic xylene solution of 1006.8 grams after the acidifying as described in the embodiment 5, measuring with potentiometry wherein has 0.16 moles of carboxylic acids.After removing these carboxylic acids with required stoichiometric sodium hydroxide (or yellow soda ash) aqueous solution, measure 0.520 mole remaining ester with vapor-phase chromatography (the total time TT of ester is 74%).Obtain uniform light yellow liquid oily crude product 206.3 grams after under reduced pressure removing removal xylene.
Distill this crude product and obtain pure products 135 grams that boiling point is 123 ℃ to 124 ℃ (under the 33.3Pa pressure).This product is the colorless liquid oily.
Analytical results and infrared spectra, nuclear magnetic resonance spectrum, mass spectroscopy all are consistent with the structure of following 'beta '-ketoester product (purity＞99%):
C
7H
15COC (C
6H
13) HC (O) OMe (molecular weight M=284)
The productive rate of the distillation pure 'beta '-ketoester in back (0.475 mole) is 64% (the ester amount with conversion is a benchmark for 1.48 moles).
Embodiment 18: obtain capryloyl benzoyl methane from 'beta '-ketoester
Equipment identical with described in the embodiment 5, but the reactor size has only 1 liter.
Add following material in the reactor:
Freshly prepd sodium methylate 43.2 grams (0.8 mole)
475 milliliters of dimethylbenzene
Mixture heating up to 140 ℃ slowly adds following 'beta '-ketoester then, carefully and up hill and dale removes the methyl alcohol that is generated simultaneously:
Capryloyl methyl caprylate 113.8 grams (0.4 mole)
The reinforced time is 1 hour 20 minutes.Find that 'beta '-ketoester changes into the enol na form quantitatively during reinforced the end.
Temperature remains 140 ℃, adds following material in 2 hour time gradually, carefully and up hill and dale removes the methyl alcohol that is generated simultaneously.
Methyl phenyl ketone 80.5 grams (0.67 mole)
When the reinforced end of methyl phenyl ketone, mixture kept 30 minutes down at 140 ℃ again.The dimethylbenzene and the carbinol mixture that are about 140 grams in existing weight of this stage distill, and wherein contain have an appointment 112 gram dimethylbenzene and about 28 gram methyl alcohol.
Comment: with the same among the embodiment 5, institute all carries out under inert nitrogen atmosphere in steps, simultaneously the additional dimethylbenzene of adding so that in the reaction mixture solvent total amount keep constant substantially.
Make reaction mixture cooling during EO, under agitation it is changed over to and be placed with 500 gram ice and 28 milliliter of 95% sulfuric acid and (contain 0.7 mole the H of having an appointment
2SO
4) beaker in.Then with embodiment 5 in the same organic phase and the aqueous phase separation of making.
Recovery obtains 675.5 gram xylene solutions, and measuring with potentiometry wherein has 0.583 mole beta-diketon functional moiety, and the chemical yield of beta-diketon is 87% (is benchmark with reinforced ketone).('beta '-ketoester is non-acid, can not disturb the potentiometric analysis in the aqueous media to measure).Also measure 0.0965 mole carboxylic acid with potentiometry.Determine following material in the reaction mixture with gas chromatographic analysis.
0.011 mole of-remaining 'beta '-ketoester
(counting 2.8%) by reinforced 'beta '-ketoester.
0.037 mole of-methyl caprylate
(counting 4.6%) by reinforced 'beta '-ketoester.
Also determine for the beta-diketon mixture and to contain following composition:
0.546 mole in-capryloyl benzoyl methane
(being equivalent to 81.5%) by reinforced ketone.
0.22 mole of-diphenylpropane-1,3-dione(DPPO)
(being equivalent to 3.3%) by reinforced ketone.
0.015 mole in-two decoyl methane
(being equivalent to 2.2%) by reinforced ketone.
After removing solvent, this reaction mixture can be directly used in the stabilization of halopolymer (as polyvinylchloride).
Embodiment 19: diphenylpropane-1,3-dione(DPPO) synthetic
The past cylindrical 2000 milliliters of reactors that are equipped with lower member:
The agitator of-belt scraping plate;
-as described in example 5 above Distallation systm; The following material of middle adding:
Freshly prepd sodium methylate 67.5 grams (1.15 moles)
800 milliliters of dimethylbenzene
Mixture heating up to 135 ℃ adds following material (in 5 fens clock times) then rapidly:
Methyl benzoate (98.5%) 151.8 gram (1.10 moles)
This medium is heated to backflow, and keeping temperature then is 135 ℃, and adds following material in 4 hour time:
Methyl phenyl ketone 120 grams (1 mole)
After the reinforced end of methyl phenyl ketone, reaction medium kept refluxing 30 minutes again, and continued to collect overhead product (vapor temperature is 70 ℃).Collect 130 milliliters of distillates altogether.
Medium is very thick, but still can stir.
Make the medium neutralization with 10% sulphuric acid soln subsequently.Through decant and washing operation, obtain solution 881 grams of diphenylpropane-1,3-dione(DPPO) in dimethylbenzene, its analytical results is 1.057 moles/kilogram, productive rate is 93.1% (is benchmark with ketone).
Embodiment 20: stearoyl benzoyl methane and palmityl benzoyl methane synthetic
Add following material in the used equipment of the embodiment that is similar to the front:
Freshly prepd sodium methylate 67.5 grams (1.15 moles)
1000 milliliters of toluene
Heated mixt to 105 ℃ adds following material then fast:
Technical pure methyl stearate 293 grams (1.03 moles)
(the ester class that contains other lipid acid, particularly
Content is 33% Uniphat A60)
This medium is heated to backflow, in 2 hour time, added following material then:
Methyl phenyl ketone 120 grams (1.0 moles)
Allow mixture reflux again 30 minutes after adding methyl phenyl ketone.In entire reaction course, collect the first benzene-methanol azeotrope (vapour temperature is 90 ℃) that comprises most of toluene continuously; The volume of collecting is 390 milliliters.Medium when reaction is finished is a homogeneous phase.Carrying out acidifying, to make the pH value be 1.Obtain solution 993 grams of beta-diketon mixture in toluene after the washing, its analytical results is 0.863 mole/kilogram, and productive rate is 85.7% (is benchmark with reinforced ketone).
After removing solvent, this reaction mixture can be directly used in the stabilization of halopolymer (as PVC).
Embodiment 21: palmityl benzoyl methane
Equipment and method as described in example 1 above, but starting material is as follows:
Freshly prepd sodium methylate 59.4 grams (1.1 moles)
715 milliliters of dimethylbenzene
Pure Uniphat A60 324.6 grams (1.2 moles)
(C
15H
31C (O) OMe, molecular weight (270.5)
Purified petroleum benzin ethyl ketone 120.0 grams (1.0 moles)
(note: palmityl benzoyl methane C
15H
31COCH
2The molecular weight of CO is 358.6).
Identical with described in the embodiment 5 of operation and method.The distillage of collecting comprises 150 gram dimethylbenzene and 62 gram methyl alcohol.
The dimethylbenzene thing washs mutually and is dry, removes volatility (removal volatile component) then to remove removal xylene.(use rotary evaporator, pressure relief is to 1995Pa during EO, and temperature is 110 ℃).
Recovery obtains the thick product of 405.6 grams, and its form is the yellow transparent solid, and fusing point is 56 ℃ to 60 ℃, wherein contains according to gas chromatographic analysis:
-palmityl benzoyl methane 290.5 grams (0.81 mole)
Molecular weight 358.6
-two palmityl methane, molecular weight 492 16.3 grams (0.033 mole)
-diphenylpropane-1,3-dione(DPPO), molecular weight 224 9.0 grams (0.04 mole)
Thereby the overall yield of beta-diketon is 0.873 mole, i.e. 87.3% (is benchmark with reinforced ketone).
Beta-diketon content is 77.9% in the crude product.
From the cold mixt of 50: 50 acetone-methyl alcohol crude product is carried out recrystallization and separate out, the recyclable 292 gram nothings that obtain are smelt white product, and its fusing point is 62 ℃ to 64 ℃, only contains the mixture of following two kinds of beta-diketons:
-palmityl benzoyl methane 276 grams
(cold material 94.5%)
-two palmityl methane 16 grams
(cold material 5.5%); Crystallization yield is about 95%.
Embodiment 22: stearoyl benzoyl methane
(C
17H
35COCH
2CO is from C
17H
35C (O) OMe)
Method as described in example 5 above, used starting material is as follows:
Freshly prepd sodium methylate 59.4 grams (1.1 moles)
715 milliliters of dimethylbenzene
Pure methyl stearate (C
17H
35CO (O) Me) 328.4 grams (1.1 moles)
Purified petroleum benzin ethyl ketone 120.05 grams (1 mole)
Obtain crude product 414.5 grams of glassy yellow solid form, its fusing point is 58 ℃ to 65 ℃.Gas chromatographic analysis shows that this product contains following composition :-stearoyl benzoyl methane, molecular weight 386.3 304 gram (0.787 mole)-distearyl methane, molecular weight 548 13.7 gram (0.025 mole)-diphenylpropane-1,3-dione(DPPO)s, molecular weight 224 7.9 gram (0.035 mole) beta-diketon total amounts 325.6 grams (0.847 mole)
Thereby total chemical yield of beta-diketon is 84.7% (0.847 mole).
The content of beta-diketon is 78.5% in the gained crude product.
From 50: 50 this crude product recrystallization is separated out, recyclable 305 grams that obtain do not have the white product of smelling flavor, and its fusing point is 67 ℃ to 69 ℃, only contains the mixture of following two kinds of beta-diketons:
-hard ester acyl benzoyl methane 291.8 grams (95.7%)
-two palmityl methane 13.2 grams (4.3%)
Crystallization yield is about 96%.
Comment: United States Patent (USP) the 5th, 015, the method for introducing among No. 777 the embodiment 10 adopt excessive greatly ester (be theoretical value 4 times), and its gained productive rate has only 45% (productive rate of 95% purity product).We are only with 10% excessive ester, and the gained chemical yield is 84.7%, the yield after the crystallization is about 80%.
Remove after the solvent, this reaction mixture can be directly used in the stabilization of halopolymer (as PVC).
Embodiment 23: capryloyl benzoyl methane
The influence of working method-add simultaneously two kinds of reactants (ester and ketone).
In order to determine it is the influence that part adds ketone and ester simultaneously and brought at least.Following two tests have been carried out with equipment described in the embodiment 5 and operation steps.
Table
Table is annotated: (1) methyl caprylate
| Test type | Starting material (mole) | Productive rate | ||||
| Initial charging | Replenish reinforced (2) | |||||
| Ester (1) | MeONa | Dimethylbenzene | COCH 3 | Ester | ||
| The reinforced simultaneously test of A contrast B | 1.20 0.200 | 1.10 1.10 | 715 milliliters 715 milliliters | 1 1.00 | - 1.00 | 89.5％ 79.7％ |
(2) in 2 hour time, added.
Test A: only add COCH
3
Test B: add COCH
3Mixture with ester.
Mensuration is carried out with potentiometry.
For the art technology present situation, progress is tangible.In fact want
About 10%.In this working method, shown in test B, MeOH can be real
Now remove continuously, but the mistake quantity not sufficient of ester is (even some ester such as 20%, adds
In initial charging).With regard to test A, allow at least 30% of the required ester of reaction
Be added in the initial charging of reactor favourable too.
Implement complete 24: different capryloyl benzoyl methane
Identical among method and the embodiment 5, but reactant is as follows:
Freshly prepd sodium methylate 62.6 grams (1.16 moles)
715 milliliters of dimethylbenzene
The isocaprylic acid methyl esters, 99% (1) 192 gram (1.20 moles)
Methyl phenyl ketone, 100% 120 grams (1.0 moles)
Described isocaprylic acid methyl esters is mainly by 3, and 5-dimethyl methyl caproate is CH
3CH
(CH
3) CH
2CH (CH
3) C (O) OCH
3Constitute.
The product analysis result is 625 milligramequivalent esters/100 grams.
Use H
2SO
4Make the reaction mixture acidifying, wash etc. after the operation, obtain solution 941.4 grams in the dimethylbenzene.
After removing dimethylbenzene, obtain 262 gram crude products, its form is even yellow oily.
It is composed as follows to record this product with potentiometry: 0.327 mole of 0.684 mole-carboxylic-acid functional of-beta-diketon functional moiety part
Comment: total chemical yield of beta-diketon is 68.4%.This numerical value is starkly lower than uses C
8The value of the ester gained of linear acid (promptly 88.7%, referring to the embodiment under the similarity condition 11).This point no wonder is because branch's ester class is with regard to COCH
2Titre not as ol ester class reactive behavior big, the heavy by product that is generated is more.
Embodiment 25: hexanoyl decoyl methane, C
5H
11COCH
2COC
7H
15
Identical among method and the embodiment 5, but reactant is as follows: freshly prepd sodium methylate 59.4 gram (1.10 moles) 715 milliliters of methyl caprylates of dimethylbenzene (linearity), 100% 189.9 gram (1.2 moles) 2-heptanone, 100% 114.2 gram (1.0 moles)
Use H
2SO
4Make the reaction mixture acidifying, carry out after the carrying out washing treatment etc., obtain solution 1069.6 grams in the dimethylbenzene of darkorange, determine with potentiometry and contain following composition: the carboxylic acid of 0.771 mole beta-diketon and 0.206 mole.
Therefore total chemical yield of beta-diketon functional moiety is 77.1%.This value is starkly lower than under similarity condition and begins resulting value (for example among embodiment 15, its productive rate is 89.5% under closely similar condition) from methyl caprylate and methyl phenyl ketone.
Therefore the selectivity of aliphatic methyl ketone (as 2-heptanone) is not as methyl phenyl ketone (aliphatic ketone has the big crotonization tendency in village).The beta-diketon mixture is carried out gas chromatographic analysis show that this mixture comprises three kinds of beta-diketons, its distribution of weight is as follows:
-two hexanoyl methane about 3.5%
-hexanoyl decoyl methane 92%
-two decoyl methane 4.5%
This reaction mixture can be directly used in the stabilization of halopolymer (as PVC) behind the removal solvent.
Embodiment 26: capryloyl benzoyl methane
The influence of working method-reaction under reduced pressure
Purpose is to determine the influence of pressure and the possibility that checking is under reduced pressure operated; Operation steps identical with described in the embodiment 8.
Table
| Test type | Operational condition | Productive rate | |||
| The reinforced time | Temperature | Solvent | Pressure | ||
| Contrast decompression (8/30 * 10 5Pa) decompression (4/30 * 10 5Pa) decompression (4/30 * 10 5Pa) decompression | 2 hours 2 hours 2 hours 5 hours | 138℃ 95℃ 77℃ 77℃ | The xylene xylene xylene xylene | 1.013×10 5Pa 2.66×10 4Pa 1.33×10 4Pa 1.33×10 4Pa | 88.7％ 91.6％ 82.3％ 89.6％ |
These tests show that reaction can carry out under low-temperature reduced-pressure.But, then should add ketone with lower feed rate if temperature drops to about 80 ℃ or be lower.
Though at length introduced embodiment preferably of the present invention here, those skilled in the art will be understood that and not break away from the scope of would stating in purport of the present invention or the appended claims, can do various variations to these embodiment.
Claims (10)
1. tasteless basically, a nontoxic liquid stabiliser composition that is used for halopolymer comprises at least two kinds of following beta-diketone compounds, and this compound is by chemical formula (I):
R
1COCH
2COR
2 (I)
And/or chemical formula (II):
R
2COCH
2COR
2 (II)
Expression, wherein
R
1By chemical formula (Y)
n-φ-expression, φ is a phenyl in the formula, each Y can be identical or different, for hydrogen atom or be selected from group with next group:
-contain hydrocarbon chain, alkoxyl group, the silyl of 1 to 12 carbon atom,
The halogen atom of-nonreactive activity;
Each R
2Can be identical or different, for hydrogen atom or be selected from group with next group:
-can be arbitrarily by the hydrocarbon chain, aralkyl, alkoxyl group or the silyl that contain 1 or 5 to 12 carbon atoms that at least one Sauerstoffatom was interrupted; And
N is an integer between 0 and 3;
If its condition is the R of chemical formula (I)
2In carbonatoms less than 5, then contained the total number of carbon atoms is at least 3 in the Y group, mostly is 12 most, and in chemical formula (II), two R
2The sum of middle carbon atom is at least 10; And
Wherein the contained beta-diketone compound of said composition is represented to have at least 2/3 corresponding with chemical formula (I) or chemical formula (II) with mole number.
2. composition as claimed in claim 1, wherein the contained beta-diketone compound of said composition is represented to have at least 3/4 corresponding with chemical formula (I) or chemical formula (II) with mole number.
3. composition as claimed in claim 1, wherein the contained beta-diketone compound of said composition is represented to have at least 4/5 corresponding with chemical formula (I) or chemical formula (II) with mole number.
4. composition as claimed in claim 1, R wherein
2Be alkyl, contained the total number of carbon atoms is less than 6 among the Y.
5. composition as claimed in claim 1, R wherein
2Be alkyl, Y and R
2In contained the total number of carbon atoms less than 12.
6. composition as claimed in claim 1, R wherein
2Be alkyl, if chain is then R of linearity
2Middle carbonatoms is between 5 to 9, if chain is branching, then R
2Middle carbonatoms is between 5 to 12.
7. composition as claimed in claim 1, wherein said composition also comprise at least a chemical formula (I) that has, other beta-diketone compound of chemical formula (II) and/or chemical formula (III):
R
1COCH
2COR
1(III) R in the formula
1And R
2Can be identical or different, it defines described in claim 1.
8. composition as claimed in claim 1, wherein said composition also further comprises at least a compound that is selected from zinc salt, alkaline earth salt and organic phosphite.
9. composition as claimed in claim 8, wherein the ratio between the quantity of beta-diketone compound total amount and said compound was at least 1: 100.
10. composition as claimed in claim 1, wherein said beta-diketon are capryloyl benzoyl methane.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9213366A FR2697838B1 (en) | 1992-11-06 | 1992-11-06 | Process for the synthesis of B diketones by a claisen condensation reaction. |
| FR9213366 | 1992-11-06 | ||
| FR9301025A FR2701024B1 (en) | 1993-02-01 | 1993-02-01 | Betadiketonic component for PVC additives, additive and PVC containing said additive. |
| FR9301025 | 1993-02-01 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98107897A Division CN1093849C (en) | 1992-11-06 | 1998-05-08 | Process for the preparation of beta-diketones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1086523A CN1086523A (en) | 1994-05-11 |
| CN1058032C true CN1058032C (en) | 2000-11-01 |
Family
ID=26229843
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93114480A Expired - Lifetime CN1058032C (en) | 1992-11-06 | 1993-11-06 | liquid stabilizer composition for halogenated polymers |
| CN98107897A Expired - Lifetime CN1093849C (en) | 1992-11-06 | 1998-05-08 | Process for the preparation of beta-diketones |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98107897A Expired - Lifetime CN1093849C (en) | 1992-11-06 | 1998-05-08 | Process for the preparation of beta-diketones |
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|---|---|
| US (2) | US5475145A (en) |
| EP (2) | EP0596809B1 (en) |
| JP (1) | JPH06228041A (en) |
| KR (1) | KR100305948B1 (en) |
| CN (2) | CN1058032C (en) |
| AT (1) | ATE242787T1 (en) |
| AU (1) | AU676689B2 (en) |
| BR (1) | BR9304656A (en) |
| CA (1) | CA2102642A1 (en) |
| CZ (1) | CZ290535B6 (en) |
| DE (1) | DE69333037T2 (en) |
| DK (1) | DK0596809T3 (en) |
| ES (1) | ES2194845T3 (en) |
| PT (1) | PT596809E (en) |
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| FR2739386B1 (en) * | 1995-10-03 | 1997-12-19 | Rhone Poulenc Chimie | COMPOSITION FOR THERMALLY STABILIZING A POLYCARBONATE COMPOSITION FOR MOLDING IN PARTICULAR BY INJECTION |
| US5925795A (en) * | 1996-09-16 | 1999-07-20 | Zeneca Limited | Processes for the preparation of aryl-β-diketones, arylpyrimidine ketones and crop protection intermediates |
| US5936129A (en) * | 1997-02-21 | 1999-08-10 | Henkel Corporation | Process for making sterically-hindered β-diketones |
| FR2816313A1 (en) * | 2000-11-03 | 2002-05-10 | Rhodia Chimie Sa | USE OF BETA DICARBONYL SILYLATED COMPOUNDS AS STABILIZERS OF HALOGENATED POLYMERS |
| US6410795B1 (en) | 2001-01-26 | 2002-06-25 | Crompton Corporation | Process for base-promoted condensation reactions and base reagent therefor |
| FR2824067A1 (en) * | 2001-03-26 | 2002-10-31 | Rhodia Chimie Sa | USE OF SUBSTITUTED DIAROMATIC B-DICETONE AS STABILIZER OF HALOGENATED POLYMERS AND POLYMER OBTAINED |
| US6872854B2 (en) * | 2002-07-03 | 2005-03-29 | Crompton Corporation | Complexes of metal salts of organic acids and beta-diketones and methods for producing same |
| FR2842519B1 (en) * | 2002-07-18 | 2007-03-16 | Rhodia Chimie Sa | PREPARATION OF BETA-DICARBONYL COMPOUNDS COMPRISING TWO SUCCESSIVE STEPS INVOLVING ALKALI AGENTS OF A DIFFERENT NATURE |
| JP2004151691A (en) * | 2002-09-30 | 2004-05-27 | Rohm & Haas Electronic Materials Llc | Improved photoresist |
| DE102004019947A1 (en) * | 2004-04-23 | 2005-11-17 | Baerlocher Gmbh | Stabilizer composition for halogen-containing thermoplastic resin compositions having improved shelf life |
| DE102004028821A1 (en) * | 2004-06-15 | 2006-01-12 | Baerlocher Gmbh | Stabilizer composition for colored halogen-containing thermoplastic resin compositions |
| FR2879610B1 (en) * | 2004-12-20 | 2007-06-15 | Rhodia Chimie Sa | STABILIZATION INGREDIENT OF HALOGEN POLYMERS COMPRISING A BETA-DICARBONYL COMPOUND |
| US20070251832A1 (en) * | 2006-04-27 | 2007-11-01 | Applied Materials, Inc. | Method and apparatus for electrochemical mechanical polishing of cu with higher liner velocity for better surface finish and higher removal rate during clearance |
| KR100741673B1 (en) | 2006-08-04 | 2007-07-25 | 테크노세미켐 주식회사 | Method for preparing 1-methoxy-2,2,6,6-tetramethyl-heptane-3,5-dione |
| CN101462930B (en) * | 2008-12-22 | 2011-09-14 | 深圳市板明科技有限公司 | Preparation of beta-dione |
| CN102503793B (en) * | 2011-11-23 | 2014-03-19 | 山东瑞丰高分子材料股份有限公司 | Preparation method of stearoylbenzoylmethane and application thereof in molding processing of thermoplastic resin |
| JP2016124939A (en) * | 2014-12-26 | 2016-07-11 | 大成化工株式会社 | Polyvinyl chloride-based sheet for medicine packaging |
| CN105273337B (en) * | 2015-11-11 | 2017-06-16 | 河北精信化工集团有限公司 | PVC organic complex Zn composite heat stabilizers and preparation method thereof |
| CN107459455B (en) * | 2016-06-02 | 2020-08-11 | 中国石化扬子石油化工有限公司 | Method for extracting methyl stearate from benzoyl methane stearate residual liquid |
| CN113943215A (en) * | 2020-07-15 | 2022-01-18 | 太原市小店区巨龙福利加工厂 | Method for preparing odorless and odorless beta-diketone |
| CN113943216A (en) * | 2020-07-15 | 2022-01-18 | 太原市小店区巨龙福利加工厂 | Process for preparing beta-diketone |
| CN115975695B (en) * | 2022-12-20 | 2024-04-16 | 武汉理工大学 | Lubricating oil composition capable of realizing wide Wen Yuchao sliding |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1086523A (en) | 1994-05-11 |
| SK281893B6 (en) | 2001-09-11 |
| US5475145A (en) | 1995-12-12 |
| SK122793A3 (en) | 1994-06-08 |
| PT596809E (en) | 2003-09-30 |
| DE69333037T2 (en) | 2004-04-01 |
| CN1232014A (en) | 1999-10-20 |
| BR9304656A (en) | 1994-07-05 |
| DE69333037D1 (en) | 2003-07-17 |
| CZ290535B6 (en) | 2002-08-14 |
| DK0596809T3 (en) | 2003-07-14 |
| ES2194845T3 (en) | 2003-12-01 |
| EP0596809B1 (en) | 2003-06-11 |
| AU676689B2 (en) | 1997-03-20 |
| CZ234593A3 (en) | 1994-05-18 |
| ATE242787T1 (en) | 2003-06-15 |
| EP0596809A1 (en) | 1994-05-11 |
| KR940011539A (en) | 1994-06-21 |
| CA2102642A1 (en) | 1994-05-07 |
| EP1229073A2 (en) | 2002-08-07 |
| EP1229073A3 (en) | 2003-03-12 |
| US5808165A (en) | 1998-09-15 |
| JPH06228041A (en) | 1994-08-16 |
| AU5037893A (en) | 1994-05-19 |
| TW360679B (en) | 1999-06-11 |
| KR100305948B1 (en) | 2001-11-30 |
| CN1093849C (en) | 2002-11-06 |
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